S.B. Atla et al. / Journal of Organometallic Chemistry 694 (2009) 683–690
689
3.1. General method for the synthesis of NC palladacycles
4.69; 1H NMR (200 MHz, CDCl3): d = 2.24 (s, 3H), 2.93–2.95 (d,
2H), 6.84–8.29 (m, 25H); 13C{1H} NMR (50.32 MHz, CDCl3):
d = (154.53, 151.47, 150.50(d, J = 2.93 Hz), 146.85, 141.57, 139.34,
137.92, 134.35(d, J = 12.07 Hz), 130.53(d, J = 2.56 Hz), 129.62,
128.83, 128.24(d, J = 10.61 Hz), 128.15, 128.05, 127.4, 126,
124.13, 122.11(d, J = 3.66 Hz), 122.03, 28.44, 21.16); 31P{1H} NMR
A mixture of the appropriate dimeric complex and triarlyphos-
phine/p-toluenesulfonic acid in chloroform was stirred at room
temperature for 15 min. The solution was filtered through celite
and hexanes were added to induce precipitation. The product
was collected by filtration and recrystallized from either CH2Cl2/
hexane or CHCl3/hexane. (The complex 4 is known so the charac-
terization details are not given).
(81.01 MHz, CDCl3): d = 32.42; IR (KBr):
m
(O@S@O) 1216 cmꢀ1
and 1154 cmꢀ1
.
3.5. [Pd (j
2-N,C-C13H11NO)(PPh3)(Cl)] (5)
3.2. [Pd (j
2-N,C-C11H8N)(PPh3)(OTs)] (1)
Yield 90%, Dec. pt. 215 °C (capillary, gradual darkening without
melting); Elemental Anal.: found: C, 62.04; H, 4.07; N, 2.34; Cl,
6.13%; C31H25ClNOPPd (600.34) Calc.: C, 62.0; H, 4.16; N, 2.33; Cl,
5.91; 1H NMR (200 MHz, CDCl3): d = 6.39–7.81 (m, 25H), 10.73 (s,
1H); 13C{1H} NMR (50.32 MHz, CDCl3): d = (166.01, 153.35,
144.75, 137.70(d, J = 10.61 Hz), 135.09(d, J = 12.08 Hz), 131.01(d,
J = 12.08 Hz), 130.75, 129.87, 129.74, 129.37, 128.76, 128.37,
128.23, 128.15, 124.24; 31P{1H} NMR (81.01 MHz, CDCl3):
d = 42.12.
Yield 92%, Dec. pt. 205 °C (capillary, gradual darkening without
melting); Elemental Anal.: found: C, 62.07; H, 4.27; N, 2.14; S,
4.14%; C36H30NO3PPdS (694.04) Calc.: C, 62.29; H, 4.32; N, 2.01;
S, 4.61; 1H NMR (200 MHz, CDCl3): d = 2.30 (s, 3H), 6.46–7.81 (m,
26H), 9.14(m, 1H); 13C{1H} NMR (125.76 MHz, CDCl3):
d = (163.10, 151.16, 148.11, 147.35, 139.59, 139.3, 139.2
135.47(d, J = 11.52 Hz), 134.74(d, J = 11.51 Hz), 130.68, 130.48,
130.09, 128.93, 128.74(d, J = 5.76 Hz), 128.21(d, J = 11.51 Hz),
126.24, 124.83, 123.98, 122.47, 118.04, 21.24); 31P{1H} NMR
(202.46 MHz, CDCl3): d = 39.92; IR (KBr):
m
(O@S@O) 1255 cmꢀ1
3.6. General procedure for the heck arylation of ethylene with BMN
and 1150 cmꢀ1
.
In a typical Heck reaction, a mixture of BMN (10.54 mmol), so-
dium acetate (15.8 mmol), solvent (NMP-23 ml) and NC palladacy-
cle catalyst (required amount, a stock solution of the catalyst in
NMP solvent was used) to make the total volume 25 cm3 were
charged into a 50 cm3 Parr Autoclave made of Hastelloy-C-276.
The reactor was purged with nitrogen to remove the traces of air
inside the reactor at room temperature and the mixtures were
heated to the desired temperature. After the temperature was at-
tained, the reactor was pressurized to 290 psi of ethylene and the
reaction was started at the agitation of 1000 rpm. The reaction
was monitored by taking aliquot samples at regular intervals and
analyzed by GC immediately. (Precaution: special care should be
taken while sampling the reaction mixtures; inorganic salts can
block the sampling tube).
3.3. [Pd (j
2-N,C-C15H10N)(PPh3)(OTs)] (2)
Yield 95%, Dec. pt. 190 °C (capillary, gradual darkening without
melting); Elemental Anal.: found: C, 59.07; H, 4.27; N, 1.44; S,
3.44%; C40H32NO3PPdS.CH2Cl2 (829.02) Calc.: C, 59.4; H, 4.13; N,
1.69; S, 3.85; 1H NMR (200 MHz, CDCl3): d = 2.14 (s, 3H), 5.29 (s,
2H), 6.47–8.59 (m, 29H); 13C{1H} NMR (50.32 MHz, CDCl3):
d = 162.82(d, J = 3.66 Hz), 150.83, 147.51(d, J = 1.83 Hz), 146.85,
141.14, 139.51, 139.28, 138.74, 135.55(d, J = 12.08 Hz), 130.79(d,
J = 2.56 Hz), 130.48, 130.34, 129.47, 128.18(d, J = 10.98 Hz), 127.7,
127.36, 126.93, 126.57, 125.78, 125.69, 124.75, 116.22, 53.40,
21.10; 31P{1H} NMR (202.46 MHz, CDCl3): d = 41.98; IR (KBR):
m
(O@S@O) 1260 cmꢀ1 and 1152 cmꢀ1
.
3.4. [Pd (
j
2-N,C-C10H8N)(PPh3)(OTs)] (3)
3.7. X-ray structure determination
Yield 90%, Dec. pt. 220 °C (capillary, gradual darkening without
melting); Elemental Anal.: found: C, 61.21; H, 4.37; N, 2.37; S,
4.35%; C35H30NO3PPdS (682.03) Calc.: C, 61.6; H, 4.4; N, 2.05; S,
The X-ray data of all the compounds were collected at room
temperature on a SMART APEX CCD single crystal X-ray diffrac-
tometer with omega and phi scan mode and different number of
Table 8
Crystallographic data for palladium complexes 1–5.
1
2
3
4
5
Formula
C36H30NO3PPdS
694.04
0.42 ꢃ 0.17 ꢃ 0.10
Monoclinic
P21/n
10.7329(4)
16.7366(7)
17.2684(7)
C41H34Cl2NO3PPdS
829.02
0.43 ꢃ 0.39 ꢃ 0.24
Monoclinic
P21/c
10.6960(5)
16.8380(8)
22.2180(9)
C35H30NO3PPdS
682.03
0.38 ꢃ 0.24 ꢃ 0.17
Monoclinic
P21/n
10.6375(4)
15.9797(6)
18.0061(7)
C29H23ClNPPd
558.30
C31H25ClNOPPd
600.34
Formula weight
Crystal size (mm)
Crystal system
Space group
a (Å)
0.50 ꢃ 0.47 ꢃ 0.33
0.13 ꢃ 0.09 ꢃ 0.05
Triclinic
Triclinic
ꢀ
ꢀ
P1
P1
9.9575(4)
10.3204(4)
13.5965(5)
78.847(1)
70.540(1)
67.960
1217.41(8)
2
9.8861(6)
10.5028(6)
14.0789(8)
75.252(1)
74.277(1)
79.892(1)
1351.84(14)
2
b (Å)
c (Å)
a
(°)
b (°)
101.608(10)
113.500(1)
95.578(1)
c
(°)
V (Å3)
3038.5(2)
4
0.770
3669.6(3)
4
0.792
3046.3(2)
4
0.767
Z
l
(mmꢀ1
)
0.955
0.869
F000
1416
1.517
1688
1.501
1392
1.487
564
1.523
608
1.475
Dcalc (g cmꢀ3
)
Number of unique reflections
5356
6462
5351
4280
4759
Number of variables
389
452
380
300
326
R
Rw
0.0320
0.0803
1.065
0.694, ꢀ0.203
0.0340
0.0897
1.062
0.849, ꢀ0.694
0.0255
0.0635
1.056
0.435, ꢀ0.171
0.0214
0.0600
1.119
0.302, ꢀ0.652
0.0278
0.0655
1.053
0.352, ꢀ0.225
Goodness-of-fit
Maximum/minimum
D
q
, e Åꢀ3